Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
  • C08J3/2053—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase
  • C08J3/2056—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase the polymer being pre-melted
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0066—Use of inorganic compounding ingredients
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0066—Flame-proofing or flame-retarding additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/02—Halogenated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
  • C08J2325/02—Homopolymers or copolymers of hydrocarbons
  • C08J2325/04—Homopolymers or copolymers of styrene

Definitions

• the invention relates to a process for the continuous introduction of solid particles into pressurized polymer melts and use in a process for the production of flame-retardant styrene polymer particle or styrene polymer extrusion foams by melt impregnation.
• halogenated flame retardants such as hexabromocyclododecane (HBCD), thermal radical formers, e.g. Dicumyl peroxide or dicumyl.
• HBCD hexabromocyclododecane
• thermal radical formers e.g. Dicumyl peroxide or dicumyl.
• thermo-sensitive additives such as flame retardants and peroxides
• the additives can be degraded and the effective amount in the product can be reduced.
• flame retardants such as HBCD can form highly corrosive hydrobromic acid
• a process for the preparation of flame-retardant, expandable polystyrene is disclosed in U.S. Pat WO 2006/007995 described, in which the residence time of the flame retardant at a melt temperature in the range of 140 to 220 ° is less than 30 minutes.
• the flame retardant synergists are metered in as liquids or in solution with a pump of a propellant-containing styrene polymer melt in the main stream. It is further proposed to premix the flame retardant with a proportion of styrene polymer melt and to meter it via a side extruder. Although this considerably shortens the time of the temperature exposure of the flameproofing agent, a premixing of the flameproofing agent in the styrene polymer melt can already be achieved thermal damage to the flame retardant occur. In addition, this process step causes additional costs.
• the object of the present invention was therefore to remedy the disadvantages mentioned and to provide a process for the simple and gentle introduction of solid particles in polymer melts.
• the process should be able to be carried out continuously and used in the production of flame-retardant, expandable styrene polymers (EPS) and flame-retardant styrene polymer extrusion foams (XPS).
• EPS expandable styrene polymers
• XPS flame-retardant styrene polymer extrusion foams
• thermoplastic polymers Melting of thermoplastic polymers is generally considered for the polymer melt. Preference is given to non-crystalline polymers having a glass transition temperature in the range from 70 to 120 ° C., particularly preferably styrene polymers.
• a rotary vane pump By means of a rotary vane pump (Orlita) surprisingly highly concentrated suspensions can be continuously required in a pressure chamber, for example a static mixer.
• the solids content of the suspension is preferably in the range from 60 to 95% by weight, more preferably in the range from 70 to 80% by weight.
• the suspended solids preferably have a D50 value determined by light scattering for the particle size in the range from 1 to 100 ⁇ m.
• the suspension has at a temperature in the range of 20 to 180 °, preferably in the range of 30 to 140 ° C, a viscosity of 10 to 1000 mPas.
• the suspension is preferably at room temperature, but can also be introduced into the polymer melt at higher temperatures depending on the viscosity.
• the suspension can go into a solution. This is done, for example, hexabromocyclododecane (HBCD) in oligomeric styrene polymers as a suspension medium.
• HBCD hexabromocyclododecane
• the suspension medium used is preferably aliphatic hydrocarbons or aliphatic hydrocarbon mixtures, for example mineral oils, medicinal white oil, pentanes or octanes.
• Suitable suspension media are also oligomeric polymers having molecular weights in the range from 500 to 5000 g / mol, in particular oligomeric styrene polymers.
• the oligomeric polymers usually have a lower plasticizing effect on the polymer matrix.
• the inventive method is particularly suitable for the gentle dosing of temperature-sensitive solid particles.
• Hexabromocyclododecane (HBCD) with a D50 value of less than 80 ⁇ m is preferably used here.
• additives for example nucleating agents, acid scavengers for decomposition products of the flame retardants, such as aluminum or magnesium hydroxides, carbon black or graphite, flame retardant synergists, for example peroxides or plasticizers, may be introduced via the suspension.
• flame retardants such as aluminum or magnesium hydroxides, carbon black or graphite
• flame retardant synergists for example peroxides or plasticizers
• the suspension can be prepared, for example, continuously by means of an intensive mixer.
• the solid particles are finely dispersed in the suspending agent.
• the supply line can contain additional mixing units and be heated.
• the process for metering flame retardants is particularly preferably used in the production of flame-retardant expandable or expanded styrene polymer particles or styrene polymer extrusion foams by melt impregnation.
• the propellant-containing styrene polymer melt can be extruded after addition of the flame retardant in the form of a suspension and optionally further additives through a die plate and cut into foam particles, or extruded through a nozzle to styrene polymer extrusion foams (XPS).
• XPS styrene polymer extrusion foams
• EPS expandable styrene polymer particles
• EPS expandable styrene polymer particles
• the process according to the invention is particularly preferably used in the production of expandable styrene polymer particles (EPS), as described below.
• EPS expandable styrene polymer particles
• the expandable styrene polymer has a molecular weight in the range of 190,000 to 400,000 g / mol, more preferably in the range of 220,000 to 300,000 g / mol. Due to the molecular weight degradation by shear and / or temperature, the molecular weight of the expandable styrene polymer is usually about 10,000 g / mol below the molecular weight of the styrene polymer used.
• the strand expansion after the nozzle exit should be as low as possible. It has been shown that the strand expansion can be influenced inter alia by the molecular weight distribution of the styrene polymer.
• the expandable styrene polymer should therefore preferably have a molecular weight distribution with a nonuniformity M w / M n of at most 3.5, more preferably in the range of 1.5 to 3 and most preferably in the range of 1.8 to 2.6.
• styrene polymers to glassy polystyrene (GPPS), toughened polystyrene (HIPS), anionically polymerized polystyrene or toughened polystyrene (A-IPS), sty-styrene- ⁇ -methstyrene copolymers, acrylonitrile-butadiene-styrene polymers (ABS), styrene-acrylonitrile (SAN ) Acrylonitrile-styrene-acrylic ester (ASA), methacrylate-butadiene-styrene (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) polymers or mixtures thereof or with polyphenylene ether (PPE) used.
• GPPS glassy polystyrene
• HIPS toughened polystyrene
• A-IPS anionically polymerized polystyrene or toughened polysty
• the styrene polymers mentioned may be used to improve the mechanical properties or the temperature resistance optionally using compatibilizers with thermoplastic polymers, such as polyamides (PA), polyolefins, such as polypropylene (PP) or polyethylene (PE), polyacrylates, such as polymethyl methacrylate (PMMA), polycarbonate ( PC), polyesters, such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polyether sulfones (PES), polyether ketones or polyether sulfides (PES) or mixtures thereof, generally in proportions of not more than 30% by weight, preferably in the range of 1 be mixed to 10 wt .-%, based on the polymer melt.
• thermoplastic polymers such as polyamides (PA), polyolefins, such as polypropylene (PP) or polyethylene (PE), polyacrylates, such as polymethyl methacrylate (PMMA), polycarbonate ( PC), polyesters, such as polyethylene
• mixtures in the above amounts ranges with z.
• rubbers such as polyacrylates or polydienes, z.
• Suitable compatibilizers are e.g. Maleic anhydride-modified styrene copolymers, polymers containing epoxy groups or organosilanes.
• the styrene polymer melt may also be mixed with polymer recyclates of the above-mentioned thermoplastic polymers, in particular styrene polymers and expandable styrene polymers (EPS), in amounts which do not substantially impair their properties, generally in amounts of not more than 50% by weight, in particular in amounts of from 1 to 20 wt .-%.
• EPS expandable styrene polymers
• the propellant-containing styrene polymer melt generally contains one or more propellants in a homogeneous distribution in a proportion of 2 to 10 wt .-%, preferably 3 to 7 wt .-%, based on the propellant-containing styrene polymer melt.
• propellants the physical ones commonly used in EPS are suitable Propellants, such as aliphatic hydrocarbons having 2 to 7 carbon atoms, alcohols, ketones, ethers or halogenated hydrocarbons. Preference is given to using isobutane, n-butane, isopentane, n-pentane.
• finely distributed internal water droplets can be introduced into the styrene polymer matrix. This can be done for example by the addition of water in the molten styrene polymer matrix. The addition of the water can be done locally before, with or after the propellant dosage. A homogeneous distribution of the water can be achieved by means of dynamic or static mixers.
• Expandable styrene polymers with at least 90% of the internal water in the form of inner water droplets with a diameter in the range of 0.5 to 15 microns form when foaming foams with sufficient cell count and homogeneous foam structure.
• the amount of blowing agent and water added is chosen so that the expandable styrene polymers (EPS) have an expansion capacity ⁇ , defined as bulk density before foaming / bulk density after foaming, at most 125, preferably 25 to 100.
• EPS expandable styrene polymers
• the expandable styrene polymer pellets generally have a bulk density of at most 700 g / l, preferably in the range of 590 to 660 g / l.
• bulk densities in the range of 590 to 1200 g / l may occur.
• organic bromine compound having a bromine content of at least 50 wt .-% can be used.
• aliphatic, cycloaliphatic and aromatic bromine compounds such as hexabromocyclododecane, pentabromochlorochlorocyclohexane, pentabromophenyl allyl ether.
• the flame retardant is generally used in amounts of 0.2 to 5, preferably from 0.5 to 2.5 wt .-%, based on the styrene polymer.
• Suitable flame retardant synergists are thermal radical formers having half lives of 6 minutes at temperatures in the range of 110 to 300 ° C, preferably 140 to 230 ° C, which are liquid or soluble in water, hydrocarbons or white oil.
• Di-tert-butyl peroxide (Trigonox® B), tert-butyl hydroperoxide (Trigonox® A80), a solution of dicumyl peroxide in pentane or an aqueous solution of a peroxide or hydroperoxide are preferably used as the flame retardant synergist.
• the flame retardant synergist is preferably used pure or in the case of solids in normal conditions (1 bar, 23 ° C) almost saturated solution, so that it can be metered with classic pumping systems directly into a temperature-controlled and pressurized space. Due to the presence in the liquid phase, a metering is possible in such a way that even quantities of low-decomposition peroxides are able to withstand sufficient amounts of the process or extrusion conditions and still achieve homogeneous mixing.
• the flame retardant synergist is used in amounts ranging from 0.05 to 1% by weight, preferably in the range from 0.1 to 0.5% by weight.
• the process according to the invention is preferably used for the production of flame-retardant, expandable styrene polymers (EPS), wherein the flame retardant is dispersed in the form of a suspension and metered into the main stream of a blowing agent-containing styrene polymer melt and extruded together through a die plate with subsequent underwater granulation.
• EPS expandable styrene polymers
• the flame retardant synergist is preferably metered directly into the main stream via a pump and metering lance at the same level or downstream.
• the residence time of the flame retardant and the flame retardant synergist can be maintained at a melt temperature in the range of 140 to 220 ° C, preferably in the range of 170 to 200 ° C at less than 10 minutes
• the styrenic polymer melt may contain additives, nucleating agents, fillers, plasticizers, soluble and insoluble inorganic and / or organic dyes and pigments, e.g. IR absorbers such as carbon black, graphite or aluminum powder together or spatially separated, e.g. be added via mixer or side extruder.
• the dyes and pigments are added in amounts ranging from 0.01 to 30, preferably in the range of 1 to 5 wt .-%.
• a dispersing aid for example organosilanes, polymers containing epoxy groups or maleic anhydride-grafted styrene polymers.
• Preferred plasticizers are mineral oils, phthalates, which can be used in amounts of from 0.05 to 10% by weight, based on the styrene polymer.
• the arrangement may include side extruders for incorporation of additives, e.g. of solids or thermally sensitive additives.
• the propellant-containing styrene polymer melt is usually conveyed through the nozzle plate at a temperature in the range from 140 to 300.degree. C., preferably in the range from 160 to 240.degree. Cooling down to the range of the glass transition temperature is not necessary.
• the nozzle plate is heated at least to the temperature of the propellant-containing styrene polymer melt.
• the temperature of the nozzle plate is in the range of 20 to 100 ° C above the temperature of the propellant-containing styrene polymer melt. This prevents polymer deposits in the nozzles and ensures trouble-free granulation.
• the diameter (D) of the nozzle bores at the nozzle exit should be in the range from 0.2 to 1.5 mm, preferably in the range from 0.3 to 1.2 mm, particularly preferably in the range from 0.3 to 0 , 8 mm lie. In this way, granule sizes of less than 2 mm, in particular in the range of 0.4 to 1.4 mm, can be set in a targeted manner even after strand expansion.
• the strand expansion can be influenced by the geometry of the die, apart from the molecular weight distribution.
• the nozzle plate preferably has bores with a ratio L / D of at least 2, the length (L) designating the nozzle region whose diameter corresponds at most to the diameter (D) at the nozzle exit.
• the ratio L / D is in the range of 3 to 20.
• the diameter (E) of the holes at the nozzle inlet of the nozzle plate should be at least twice as large as the diameter (D) at the nozzle outlet.
• An embodiment of the nozzle plate has bores with conical inlet and an inlet angle ⁇ less than 180 °, preferably in the range of 30 to 120 °.
• the nozzle plate has bores with conical outlet and an outlet angle ⁇ less than 90 °, preferably in the range of 15 to 45 °.
• the nozzle plate can be equipped with bores of different exit diameters (D). The various embodiments of the nozzle geometry can also be combined.
• the granulation can be carried out directly behind the nozzle plate under water at a pressure in the range of 1 to 25 bar, preferably 5 to 15 bar.
• EPS expandable styrene polymers
• Shear rates below 50 / sec, preferably 5 to 30 / sec, and temperatures below 260 ° C. and short residence times in the range from 1 to 20, preferably 2 to 10 minutes in stages d) to f) are therefore particularly preferred.
• the polymer melt can be pumped and discharged by pressure pumps, eg gear pumps.
• a further possibility for reducing the styrene monomer content and / or residual solvents, such as ethylbenzene, is to provide high degassing by means of entrainers, for example water, nitrogen or carbon dioxide, in step b) or to carry out the polymerization step a) anionically.
• entrainers for example water, nitrogen or carbon dioxide
• the final expandable styrenic polymer granules may be coated by glycerol esters, antistatic agents or anticaking agents.
• the EPS granules may be coated with glycerol monostearate GMS (typically 0.25%), glycerol tristearate (typically 0.25%) finely divided silica Aerosil R972 (typically 0.12%) and Zn stearate (typically 0.15%), and antistatic ,
• the expandable styrene polymer granules can be prefoamed in a first step by means of hot air or steam to foam particles having a density in the range of 8 to 100 g / l and welded in a second step in a closed mold to particle moldings.
• temperature-sensitive additives in particular flame retardants
• flame retardants can be incorporated gently and homogeneously into a polymer melt.
• the amount of temperature-sensitive additives used can be reduced or the effective amount in the product can be increased. Due to the careful incorporation of flame retardants, the use of flame retardant synergists is not absolutely necessary for adequate flame retardancy.
• a blowing agent-containing polymer melt (polystyrene 158 K, 3.6 wt .-% graphite and 6.5 wt .-% n-pentane) was after cooling from 260 ° C to 180 ° C by means of a rotary vane pump 2.55 wt. - Mixed% of a suspension of 70 wt .-% HBCD and 30 wt .-% white oil.
• Dicumyl peroxide as a flame retardant synergist dissolved in pentane was metered into the cooled main stream via a piston pump and metering lance downstream.
• the resulting graphite, propellant flame retardant, and synergist-containing polymer melt was fed through a die plate with 32 holes (0.75 mm diameter) at a throughput of 60 kg / hr and granulated to compact granules of narrow size distribution using pressurized underwater granulation ,
• a blowing agent-containing polymer melt (polystyrene 158 K and 7 wt .-% n-pentane) was after cooling from 260 ° C to 190 ° C via a piston pump in white oil suspended hexabromocyclododecane (HBCD) according to the information in Table 1 (added amounts in weight percent, based on polystyrene) added.
• HBCD white oil suspended hexabromocyclododecane
• the resulting polymer melt was conveyed through a nozzle plate with 32 bores (0.75 mm diameter) at a throughput of 60 kg / h and with the aid of a pressurized underwater granulation granulated into compact granules with narrow size distribution.
• a blowing agent-containing polymer melt (polystyrene 158 K, 3.6 wt .-% graphite and 6.5 wt .-% n-pentane) was after cooling from 260 ° C to 180 ° C via a side extruder in a polystyrene melt premixed Hexabromcyclododekan (HBCD) (1.8 wt .-% HBCD, 3.6 wt .-% polystyrene based on main stream) added.
• HBCD Hexabromcyclododekan
• Dicumyl peroxide was added downstream as a flame retardant synergist via a piston pump and metering lance.
• the resulting polymer melt was passed through a nozzle plate with 32 holes (0.75 mm diameter) at a throughput of 60 kg / h and granulated by means of a pressurized underwater granulation to form compact granules with a narrow size distribution.
• a propellant-containing polymer melt (polystyrene 158 K, 3.6 wt .-% graphite and 6.5 wt .-% n-pentane) was after cooling from 260 ° C to 180 ° C by means of a rotary vane pump 3.3 wt. -% of a solution (formed from a suspension by heating to 160 ° C) from 60 wt .-% HBCD and 40 wt .-% Joncryl ADF 1300 mixed.
• the resulting graphite, propellant and flame retardant-containing polymer melt was conveyed at a throughput of 60 kg / h through a nozzle plate with 32 bores (0.75 mm diameter) and granulated using a pressurized underwater granulation to form compact granules with a narrow size distribution.
• a blowing agent-containing polymer melt (polystyrene 158 K, 3.6 wt .-% graphite and 6.5 wt .-% n-pentane) was after cooling from 260 ° C to 180 ° C via a side extruder in a polystyrene melt premixed Hexabromcyclododekan (HBCD) (1.4 wt .-% HBCD, 2.8 wt .-% polystyrene based on main stream) added. Dicumyl peroxide was added downstream as a flame retardant synergist via a piston pump and metering lance.
• HBCD Hexabromcyclododekan
• the resulting polymer melt was passed through a nozzle plate with 32 holes (0.75 mm diameter) at a throughput of 60 kg / h and granulated by means of a pressurized underwater granulation to form compact granules with a narrow size distribution.
• the resulting expandable polystyrene granules were prefoamed in flowing steam to form foam particles having a density of about 20 g / l and, after storage for 24 hours in gas-tight forms, welded to foam bodies with steam.
• Table 1 The amount of flame retardant (dosage) as well as the results of the fire protection test and the viscosity number VZ, measured in the EPS particle foam, are summarized in Table 1.
• Table 1 example HBCD [% by weight] Synergist [wt%] synergist Flame retardant test B2 PS VZ 1 1.8 - - ++ 158 K 2 1.6 - - ++ 158 K 3 1.4 + 158 K 4 2.0 0.4
• Perkadox 30 + 158 K 85 5 1.2 - - + 158 K 86 6 2.0 ++ 158 K V1 1.8 + 158 K V2 1.4 - 158 K

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• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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• Compositions Of Macromolecular Compounds (AREA)
• Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

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• 2008
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